



Patented Nov. 15, 1932 UNITED STATES ERNEST r. GRETHER, or MIDLAND, MIoIIIeAN,, AssIGNoI%.ro new ci'IEMIcAI;

COMPANY, or MIDLAND, MICHIGAN, coaron rIo or MICHIGAN a, f

ALKYL mum on IIALOGENATED PARA- YDMXYDIPIIENYLS No Drawing. Original application filed October 11, 1928,- Seria'l 3 16- 311,97. iliv ided and this filed December 6, 1929. Serial I0. 41%?921;

chemical curiosities without practical significance.

In a previous application, Serial No. 311,- 976, filed October 11, 1928 now Patent No. 1,882,484, of which this is a division I have described new and useful derivatives of 4- hydroxy-diphenyl and specifically claimed chloro-hydroxy-diphenyls. In the present application, I shall claim certain other new and useful compounds derived from the above mentioned l-hydroxy-diphenyl, par

ticularly the alkoxy halogenated derivatives,

as well as useful and novelmethods for the preparation thereof.

To the accomplishment of the foregoing and related ends, the invention, then, consists of the methods and products hereinafter fully described and particularly pointed out in the claims, such methods and products, however, constituting but several of the ways and products respectively in which the principle of the invention may be exemplified.

' I have found that the aforesaid 4-hydroxydiphenyl may be halogenated under suitably controlled conditions whereby the mono-, dior higher halogenated derivatives are obtained. I am aware that bromo derivatives have previously been prepared, as well as certain nitro and amino derivatives. However, none of the chlor-derivatives have been described in the literature.

I have further found that the alkyl ethers of the above mentioned halo derivatives of l-hydroxy-diphenyl may be prepared by treating with alkylating agents in the usual way, for instance by reacting such with either a dialky] sulfate or an alkyl halide.

application Representative compound of 1-,h@ i 1;

types in question, as well as suitable methods for thepreparatlon thereof, are described in the following examples 7 1. 3 chlor-bhydroxy diph n l,

One mole 4-hydroxy-diphenyl is dissolved in one mole caustic soda and six liters water, the solution cooled and a solution containing one mole sodium hypochlorite added slowly with constant stirring. The reaction mixture is allowed to stand for-about one hour, then warmed to, about40 Q, filtered, and, after cooling, the 3-chlor-compound precipitated from' the filtrate with hydrochloric acid. 7'

Fine colorless crystals, M. P. 7 7 G; 2; 3 chlor t-methoxy-diphenyl.

J An alkaline solution of the preceding compound is treated with-one; and one-eighth mole methyl sulphate, with stirring; The methyl ether precipitates out. r'l-o eo'r'fiplete the reaction the mixture is warmed to 50 to C. for about one-half houmthen cooled and the crystals filtered off.- Fine colorless crystals, M. P.'91 to 92 3. 3-brom-inethoxy diphenyli OGHi Formed by similar method to arid Fine colorless crystals,- M. F; 61. ftofivit C;

' The foregoing specific examples are merely illustrative of certain convenient methods of procedure for the preparation of the general classes of compounds herein referred to. While in some of the examples the formation of a methyl etheris described, it is equally feasible to prepare an ethyl or other alkyl ether by the use of an appropriate alkylating agent. Furthermore, I do not limit myself to the specific reagents as stated in the examples, for other related compounds in certain cases are adapted to the type of reaction in question and mav be used, if desired, to prepare products of the above general description. For example, instead of sodium hypochlorite as chlorinating agent, I -may f use calcium, or other hypochlorite, or chlorine gas. For the formation of a mono-chlor de-' rivative, a hypochlorite solution is to be preferred, whereas with chlorine'directly the tendency is toward the production of dior higher chlorinated derivatives. Likewise brominated derivatives may be made by employing the corresponding brominating agents. While methyl sulphate is specifically referred to in the example, I may use other methylating, or alkylating agents, such as a methyl or alkyl halide. It is also evident that, in some cases at least, thesequence of operations may be variedv without change in the end-product obtained.

Other modes of applying the principle of the invention may be employed instead of the one explained,*change being made as regards the method herein disclosed, provided the step or steps and ingredients stated-by any of the following claims, or the equivalent of such be employed.

I'therefore particularly point out and distinctly claim as my invention 1. The method of making a derivative of l-hydroxy-diphenyl, which comprises alkylating the hydroxyl group of a halogenated 4-hydroXy-dipheny1 containing at least one halogen group. i

2. The method of making a derivative of -hydroxy-diphenyl, which comprises alkylating the hydroxyl group of a chlorinated 4c-hydroxy-diphenyl containing at least one chlorine group.

3. The method ofmaking 3.4-chloro-alkoxy-diphenyl, which comprises alkylatin 3.4-chloro-hydroxy-diphenyl.

4-. The method of making '3A-chloro methoXy-diphenyl, which comprises methylating 3.4 chloro hydroXy-diphenyl.

5. As a new product, an alkyl ether of 3.4-

halo-hydroxy-diphenyl.

6. As a new product, an alkyl ether of 3.4- A I chloro-hydroxy-diphenyl.

7. As a new product, 3.4-chloro-methoxydiphenyl having a meltingpointof about 91 to 92 (1, and being obtainable in colorless crystals; I

8. As a newproduct, 3.4-bromo-methoxydiphenyl having a melting point of about 61 to 63 ERNEST F. GRETHER.

:Signed by me this 29th day of November, 

